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Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR
Published on: December 16, 2013
Electronic Structure Studies on the Whole Keplerate Family: Predicting New Members
Dolores Melgar1, Nuno A G Bandeira1, Carles Bo1,2
1Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. dels Països Catalans, 16, 43007, Tarragona, Spain.
Abstract:
A comprehensive study of the electronic structure of nanoscale molecular oxide capsules of the type [{MVI (MVI )5 O21 }12 {M'V2 O2 (μ-X)(μ-Y)(Ln- )}30 ](12+n)- is presented, where M,M'=Mo,W, and the bridging ligands X,Y=O,S, carried out by means of density functional theory. Discussion of the electronic structure of these derivatives is focused on the thermodynamic stability of each of the structures, the one having the highest HOMO-LUMO gap being M=W, M'=Mo, X=Y=S. For the most well-known structure M=M'=Mo, X=Y=O, [Mo132 O372 ]12- , the chemical bonding of several ligands to the {MoV2 O2 (μ-O)2 } linker moiety produces negligible effects on its stability, which is evidence of a strong ionic component in these bonds. The existence of a hitherto unknown species, namely W132 with both bridging alternatives, is discussed and put into context.
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